Abstract
Due to the inherent advantages of cellulose derivatives, there has been a dedicated focus in research to employ them as alternatives to synthetic materials. In this study, we investigated the potential of cellulose acetate sulfate (CAS) for the film fabrication, exploring how the properties of CAS films vary in relation to the number of sulfate groups (DSsulfate). CAS films with different DSsulfate (0.4, 0.7, and 1.0) were prepared using solvent casting. Despite variations in DSsulfate, all CAS produced transparent and self-supporting films. Nonetheless, the characteristics of CAS films were found to be significantly influenced by their DSsulfate. Owing to the size of sulfate groups, the substitution of these groups induces alterations in the polymer networks present within CAS films. These alterations, combined with the hydrophilic nature of sulfate groups, give rise to distinct variations in the characteristics of films associated with DSsulfate. CAS films with the lowest DSsulfate (0.4) demonstrated superior mechanical properties with an elastic modulus of 2131.6 MPa and tensile strength of 36.7 MPa. Conversely, higher DSsulfate correlated with increased wettability and water vapor permeability (WVP). CAS films with the highest DSsulfate exhibited maximum wettability (43.2°) and WVP (2.58 × 10–10 g·s−1·m−1·Pa−1). These findings, given the limited research on CAS characteristics, hold the potential to expand horizons in the selection of eco-friendly materials based on cellulose derivatives.
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Adilah AN, Jamilah B, Noranizan MA, Hanani ZAN (2018) Utilization of mango peel extracts on the biodegradable films for active packaging. Food Packag Shelf Life 16:1–7. https://doi.org/10.1016/j.fpsl.2018.01.006
Aguirre-Loredo RY, Rodríguez-Hernández AI, Morales-Sánchez E et al (2016) Effect of equilibrium moisture content on barrier, mechanical and thermal properties of chitosan films. Food Chem 196:560–566. https://doi.org/10.1016/j.foodchem.2015.09.065
Ansari S, Rashid MdAI, Waghmare PR, Nobes DS (2020) Measurement of the flow behavior index of Newtonian and shear-thinning fluids via analysis of the flow velocity characteristics in a mini-channel. SN Appl Sci 2:1787. https://doi.org/10.1007/s42452-020-03561-w
Arfin T (2020) Chapter 12 - Cellulose and hydrogel matrices for environmental applications. In: Mohammad F, Al-Lohedan HA, Jawaid M (eds) Sustainable nanocellulose and nanohydrogels from natural sources. Elsevier, pp 255–274
Asbury JB, Steinel T, Fayer MD (2004) Hydrogen bond networks: structure and evolution after hydrogen bond breaking. J Phys Chem B 108:6544–6554. https://doi.org/10.1021/jp036600c
Asim N, Badiei M, Mohammad M (2021) Recent advances in cellulose-based hydrophobic food packaging. Emergent Mater. https://doi.org/10.1007/s42247-021-00314-2
Assis RQ, Rios PD, de Rios A, O, Olivera FC, (2020) Biodegradable packaging of cellulose acetate incorporated with norbixin, lycopene or zeaxanthin. Ind Crops Prod 147:112212. https://doi.org/10.1016/j.indcrop.2020.112212
Atiwesh G, Mikhael A, Parrish CC et al (2021) Environmental impact of bioplastic use: a review. Heliyon 7:e07918. https://doi.org/10.1016/j.heliyon.2021.e07918
Azaza YB, Hamdi M, Charmette C et al (2023) Development and characterization of composite films based on chitosan and collagenous proteins from bluefin tuna: application for peeled shrimp preservation. Cellulose 30:373–395. https://doi.org/10.1007/s10570-022-04893-z
Biswas A, do Socorro Rocha Bastos M, Furtado RF, et al (2020) Evaluation of the properties of cellulose ester films that incorporate essential oils. Int J Polym Sci 2020:e4620868. https://doi.org/10.1155/2020/4620868
Boarino A, Klok H-A (2023) Opportunities and challenges for lignin valorization in food packaging, antimicrobial, and agricultural applications. Biomacromol 24:1065–1077. https://doi.org/10.1021/acs.biomac.2c01385
Bonifacio A, Bonetti L, Piantanida E, De Nardo L (2023) Plasticizer design strategies enabling advanced applications of cellulose acetate. Eur Polym J 197:112360. https://doi.org/10.1016/j.eurpolymj.2023.112360
Brandrup J, Immergut EH, Grulke EA (eds) (1999) Polymer handbook, 4th edn. Wiley, New York
Bustamante-Torres M, Romero-Fierro D, Arcentales-Vera B et al (2021) Hydrogels classification according to the physical or chemical interactions and as stimuli-sensitive materials. Gels Basel Switz 7:182. https://doi.org/10.3390/gels7040182
Cadek M, Coleman JN, Barron V et al (2002) Morphological and mechanical properties of carbon-nanotube-reinforced semicrystalline and amorphous polymer composites. Appl Phys Lett 81:5123–5125. https://doi.org/10.1063/1.1533118
Calvino C, Macke N, Kato R, Rowan SJ (2020) Development, processing and applications of bio-sourced cellulose nanocrystal composites. Prog Polym Sci 103:101221. https://doi.org/10.1016/j.progpolymsci.2020.101221
Cao Y, Mu T (2014) Comprehensive investigation on the thermal stability of 66 ionic liquids by thermogravimetric analysis. Ind Eng Chem Res 53:8651–8664. https://doi.org/10.1021/ie5009597
Charpentier D, Mocanu G, Carpov A et al (1997) New hydrophobically modified carboxymethylcellulose derivatives. Carbohydr Polym 33:177–186. https://doi.org/10.1016/S0144-8617(97)00031-3
Chauvelon G, Doublier J-L, Buléon A et al (2003) Rheological properties of sulfoacetate derivatives of cellulose. Carbohydr Res 338:751–759. https://doi.org/10.1016/S0008-6215(03)00009-0
Chen G, Zhang B, Zhao J, Chen H (2014) Development and characterization of food packaging film from cellulose sulfate. Food Hydrocoll 35:476–483. https://doi.org/10.1016/j.foodhyd.2013.07.003
Chen Q, Liu Y, Chen G (2019) A comparative study on the starch-based biocomposite films reinforced by nanocellulose prepared from different non-wood fibers. Cellulose 26:2425–2435. https://doi.org/10.1007/s10570-019-02254-x
Cichosz S, Masek A (2020) IR study on cellulose with the varied moisture contents: insight into the supramolecular structure. Materials 13:4573. https://doi.org/10.3390/ma13204573
Das D, Panesar PS, Saini CS, Kennedy JF (2022) Improvement in properties of edible film through non-thermal treatments and nanocomposite materials: a review. Food Packag Shelf Life 32:100843. https://doi.org/10.1016/j.fpsl.2022.100843
Faure C, Tranchant JF, Dufourc EJ (1996) Comparative effects of cholesterol and cholesterol sulfate on hydration and ordering of dimyristoylphosphatidylcholine membranes. Biophys J 70:1380–1390. https://doi.org/10.1016/S0006-3495(96)79696-0
Forgiarini A, Scorzza C, Velásquez J et al (2010) Influence of the mixed propoxy/ethoxy spacer arrangement order and of the ionic head group nature on the adsorption and aggregation of Extended surfactants. J Surfactants Deterg 13:451–458. https://doi.org/10.1007/s11743-010-1216-5
Galus S (2018) Functional properties of soy protein isolate edible films as affected by rapeseed oil concentration. Food Hydrocoll 85:233–241. https://doi.org/10.1016/j.foodhyd.2018.07.026
Galus S, Arik Kibar EA, Gniewosz M, Kraśniewska K (2020) Novel materials in the preparation of edible films and coatings—A review. Coatings 10:674. https://doi.org/10.3390/coatings10070674
Ganapathy V, Muthukumaran G, Sudhagar PE et al (2023) Mechanical properties of cellulose-based multiscale composites: a review. Polym Compos 44:734–756. https://doi.org/10.1002/pc.27175
Garusinghe UM, Varanasi S, Raghuwanshi VS et al (2018) Nanocellulose-montmorillonite composites of low water vapour permeability. Colloids Surf Physicochem Eng Asp 540:233–241. https://doi.org/10.1016/j.colsurfa.2018.01.010
Grant D, Long WF, Moffat CF, Williamson FB (1991) Infrared spectroscopy of heparins suggests that the region 750–950 cm-1 is sensitive to changes in iduronate residue ring conformation. Biochem J 275(Pt 1):193–197. https://doi.org/10.1042/bj2750193
Guan T, Miao Y, Xu L et al (2011) Injectable nimodipine-loaded nanoliposomes: preparation, lyophilization and characteristics. Int J Pharm 410:180–187. https://doi.org/10.1016/j.ijpharm.2011.03.009
Guzman-Puyol S, Benítez JJ, Heredia-Guerrero JA (2022a) Transparency of polymeric food packaging materials. Food Res Int 161:111792. https://doi.org/10.1016/j.foodres.2022.111792
Guzman-Puyol S, Hierrezuelo J, Benítez JJ et al (2022b) Transparent, UV-blocking, and high barrier cellulose-based bioplastics with naringin as active food packaging materials. Int J Biol Macromol 209:1985–1994. https://doi.org/10.1016/j.ijbiomac.2022.04.177
Hafiezal MRM, Khalina A, Zurina ZA et al (2019) Thermal and flammability characteristics of blended jatropha bio-epoxy as matrix in carbon fiber-reinforced polymer. J Compos Sci 3:6. https://doi.org/10.3390/jcs3010006
Hambleton A, Voilley A, Debeaufort F (2011) Transport parameters for aroma compounds through i-carrageenan and sodium alginate-based edible films. Food Hydrocoll 25:1128–1133. https://doi.org/10.1016/j.foodhyd.2010.10.010
Hassanloofard Z, Gharekhani M, Zandi M et al (2023) Fabrication and characterization of cellulose acetate film containing Falcaria vulgaris extract. Cellulose 30:6833–6853. https://doi.org/10.1007/s10570-023-05337-y
Heinze T, El Seoud OA, Koschella A (2018) Structure and properties of cellulose and its derivatives. In: Heinze t, El Seoud OA, Koschella A (eds) Cellulose derivatives: synthesis, structure, and properties. Springer International Publishing, Cham, pp 39–172
Hettrich K, Wagenknecht W, Volkert B, Fischer S (2008) New possibilities of the acetosulfation of cellulose. Macromol Symp 262:162–169. https://doi.org/10.1002/masy.200850216
Ibrahim M, Fahmy T, Salaheldin E et al (2015) Role of tosyl cellulose acetate as potential carrier for controlled drug release. Life Sci J 12:127–133. https://doi.org/10.7537/marslsj121015.16
Ilyas RA, Sapuan SM, Ibrahim R et al (2019) Effect of sugar palm nanofibrillated cellulose concentrations on morphological, mechanical and physical properties of biodegradable films based on agro-waste sugar palm (Arenga pinnata (Wurmb.) Merr) starch. J Mater Res Technol 8:4819–4830. https://doi.org/10.1016/j.jmrt.2019.08.028
Jiang Z, Ngai T (2022) Recent advances in chemically modified cellulose and its derivatives for food packaging applications: a review. Polymers 14:1533. https://doi.org/10.3390/polym14081533
Kaushik A, Kaur R (2016) Thermoplastic starch nanocomposites reinforced with cellulose nanocrystals: effect of plasticizer on properties. Compos Interfaces 23:701–717. https://doi.org/10.1080/09276440.2016.1169487
Kaya EC, Yucel U, Kaya EC, Yucel U (2023) Advances in cellulose-based packaging films for food products. In: Cellulose–Fundamentals and conversion into biofuel and useful chemicals. IntechOpen
Klemm D, Philipp B, Heinze T et al (1998) Comprehensive cellulose chemistry: functionalization of cellulose, 1st edn. Wiley
Kowalczyk D, Baraniak B (2014) Effect of candelilla wax on functional properties of biopolymer emulsion films–A comparative study. Food Hydrocoll 41:195–209. https://doi.org/10.1016/j.foodhyd.2014.04.004
Kumar S, Aswal DK (2020) Thin film and significance of its thickness. In: Kumar S, Aswal DK (eds) Recent advances in thin films. Springer, Singapore, pp 1–12
la Vega AS, Salazar-Lozas H, Narváez WEV et al (2021) Water clusters as bifunctional catalysts in organic chemistry: the hydrolysis of oxirane and its methyl derivatives. Org Biomol Chem 19:6776–6780. https://doi.org/10.1039/D1OB01026C
Law K-Y (2014) Definitions for hydrophilicity, hydrophobicity, and superhydrophobicity: getting the Basics Right. J Phys Chem Lett 5:686–688. https://doi.org/10.1021/jz402762h
Liu Y, Ahmed S, Sameen DE et al (2021) A review of cellulose and its derivatives in biopolymer-based for food packaging application. Trends Food Sci Technol 112:532–546. https://doi.org/10.1016/j.tifs.2021.04.016
Luecke H, Quiocho FA (1990) High specificity of a phosphate transport protein determined by hydrogen bonds. Nature 347:402–406. https://doi.org/10.1038/347402a0
Malhotra B, Keshwani A, London HK (2015) Natural polymer based cling films for food packaging. Int J Pharm Pharm Sci 7:10–18
Marrez DA, Abdelhamid AE, Darwesh OM (2019) Eco-friendly cellulose acetate green synthesized silver nano-composite as antibacterial packaging system for food safety. Food Packag Shelf Life 20:100302. https://doi.org/10.1016/j.fpsl.2019.100302
Masek A, Kosmalska A (2022) Technological limitations in obtaining and using cellulose biocomposites. Front Bioeng Biotechnol 10:912052. https://doi.org/10.3389/fbioe.2022.912052
Matta E, Tavera-Quiroz MJ, Bertola N (2019) Active edible films of methylcellulose with extracts of green apple (Granny Smith) skin. Int J Biol Macromol 124:1292–1298. https://doi.org/10.1016/j.ijbiomac.2018.12.114
Mu R, Hong X, Ni Y et al (2019) Recent trends and applications of cellulose nanocrystals in food industry. Trends Food Sci Technol 93:136–144. https://doi.org/10.1016/j.tifs.2019.09.013
Oprea M, Voicu SI (2020) Recent advances in composites based on cellulose derivatives for biomedical applications. Carbohydr Polym 247:116683. https://doi.org/10.1016/j.carbpol.2020.116683
Park S, Yoo S, Cho S-M et al (2023) Production of single-component cellulose-based hydrogel and its utilization as adsorbent for aqueous contaminants. Int J Biol Macromol. https://doi.org/10.1016/j.ijbiomac.2023.125085
Rohowsky J, Heise K, Fischer S, Hettrich K (2016) Synthesis and characterization of novel cellulose ether sulfates. Carbohydr Polym 142:56–62. https://doi.org/10.1016/j.carbpol.2015.12.060
Romão S, Bettencourt A, Ribeiro IAC (2022) Novel features of cellulose-based films as sustainable alternatives for food packaging. Polymers 14:4968. https://doi.org/10.3390/polym14224968
Salari M, Sowti Khiabani M, Rezaei Mokarram R et al (2021) Use of gamma irradiation technology for modification of bacterial cellulose nanocrystals/chitosan nanocomposite film. Carbohydr Polym 253:117144. https://doi.org/10.1016/j.carbpol.2020.117144
Salim MH, Abdellaoui Y, Ait Benhamou A et al (2022) Influence of cellulose nanocrystals from pea pod waste on mechanical, thermal, biodegradability, and barrier properties of chitosan-based films. Cellulose 29:5117–5135. https://doi.org/10.1007/s10570-022-04587-6
Seddiqi H, Oliaei E, Honarkar H et al (2021) Cellulose and its derivatives: towards biomedical applications. Cellulose 28:1893–1931. https://doi.org/10.1007/s10570-020-03674-w
Selberg J, Jia M, Rolandi M (2019) Proton conductivity of Glycosaminoglycans. PLOS ONE 14:e0202713. https://doi.org/10.1371/journal.pone.0202713
Shah YA, Bhatia S, Al-Harrasi A et al (2023) Mechanical properties of protein-based food packaging materials. Polymers 15:1724. https://doi.org/10.3390/polym15071724
Sharma A, Mandal T, Goswami S (2021) Fabrication of cellulose acetate nanocomposite films with lignocelluosic nanofiber filler for superior effect on thermal, mechanical and optical properties. Nano-Struct Nano-Objects 25:100642. https://doi.org/10.1016/j.nanoso.2020.100642
Song J, Birbach N, Hinestroza J (2012) Deposition of silver nanoparticles on cellulosic fibers via stabilization of carboxymethyl groups. Cellulose. https://doi.org/10.1007/s10570-011-9647-3
Sorolla-Rosario D, Llorca-Porcel J, Pérez-Martínez M et al (2022) Study of microplastics with semicrystalline and amorphous structure identification by TGA and DSC. J Environ Chem Eng 10:106886. https://doi.org/10.1016/j.jece.2021.106886
Swaroop K, Gaana MJ, Shruthi SS et al (2019) Studies on swelling behaviour of radiolytically synthesised PVA/gelatin hydrogels. AIP Conf Proc 2115:030050. https://doi.org/10.1063/1.5112889
Tanaka R, Meadows J, Phillips GO, Williams PA (1990) Viscometric and spectroscopic studies on the solution behaviour of hydrophobically modified cellulosic polymers. Carbohydr Polym 12:443–459. https://doi.org/10.1016/0144-8617(90)90093-8
Thomas A (2014) Application of nanotechnolog in food and dairy industry. Indian J Dairy Sci 67:367–374
Vergne P (2007) 23 - super low traction under EHD & mixed lubrication regimes. In: Erdemir A, Martin J-M (eds) Superlubricity. Elsevier Science B.V, Amsterdam, pp 427–443
Yang Z, Lu S, Lan L et al (2019) Twelve-coordinated sulfate hydrogen bonding interactions in water-containing Fe(II) system. Mol Cryst Liq Cryst 680:96–104. https://doi.org/10.1080/15421406.2019.1624400
Zhang K, Peschel D, Bäucker E et al (2011) Synthesis and characterisation of cellulose sulfates regarding the degrees of substitution, degrees of polymerisation and morphology. Carbohydr Polym 83:1659–1664. https://doi.org/10.1016/j.carbpol.2010.10.029
Zhang J, Xu W-R, Zhang Y et al (2018a) Liquefied chitin/polyvinyl alcohol based blend membranes: preparation and characterization and antibacterial activity. Carbohydr Polym 180:175–181. https://doi.org/10.1016/j.carbpol.2017.10.014
Zhang S, Kim N, Yokoyama W, Kim Y (2018b) Effects of moisture content on mechanical properties, transparency, and thermal stability of yuba film. Food Chem 243:202–207. https://doi.org/10.1016/j.foodchem.2017.09.127
Zhang J, Guo Z, Chen S et al (2021) High-barrier, strong, and antibacterial paper fabricated by coating acetylated cellulose and cinnamaldehyde for food packaging. Cellulose 28:4371–4384. https://doi.org/10.1007/s10570-021-03778-x
Zhao J, Wang Y, Liu C (2022) Film transparency and opacity measurements. Food Anal Methods 15:2840–2846. https://doi.org/10.1007/s12161-022-02343-x
Zhou H, Tong H, Lu J et al (2021) Preparation of bio-based cellulose acetate/chitosan composite film with oxygen and water resistant properties. Carbohydr Polym 270:118381. https://doi.org/10.1016/j.carbpol.2021.118381
Zhou L, Liu X, Jiang S et al (2023) In-situ microstructure regulation towards feasible production of self-reinforced lignocellulose nanopaper with multifunctionality. Ind Crops Prod 193:116229. https://doi.org/10.1016/j.indcrop.2022.116229
Acknowledgments
The authors would like to extend their gratitude to Eastman Chemical Company for generously providing cellulose acetate with a DSacetyl of 1.8.
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This study was supported by Eastman Chemical Company (EMN -13-S-E-XX-S-2016-2048).
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SP contributed to the conceptualization, methodology, lead investigation, analysis, visualization, writing-original draft, reviewing, and editing. SY contributed to the conceptualization, methodology, analysis, and writing-original draft. S-MC contributed to the methodology, analysis, and writing-original draft. HP contributed to the methodology and analysis. DC contributed to the methodology and analysis. SSK and SP contributed to the conceptualization, supervision, validation, discussion, and draft review.
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Park, S., Yoo, S., Cho, SM. et al. Exploring potential of cellulose acetate sulfate films for sustainable packaging: tuning characteristics via sulfate group variation. Cellulose 31, 1755–1772 (2024). https://doi.org/10.1007/s10570-023-05713-8
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DOI: https://doi.org/10.1007/s10570-023-05713-8